Zirconium-hafnium separation process



March 27, 1951 K. STREET, JR 2,546'953 zIRcoNIuM-HAFNIUM sEPARATIoN PRocEss Filed Nov. 25, 1949 MILLIGRAMS OXIDE PER MILLILITER l 1 I I 1 I 20 40 60 80 IOO IZO |40 MILLILITERS OF ELUTRIANT INVENTOR. KE/vA/ETH STREET, L/f'.

' Patented Mar. 27, 1951 uNrri-:o srATEs PATENT OFFICE ZIRCONI-UM-HAFNIUIWF SEPARATION PROCES S=` Kenneth Street, J r., Berkeley, Calif., assi'gnor to. the United'- States ofAmerica; as'represented by the United' States Atomic Energy' Commission Application November 25, 1949, Serial No. 1293267 (Cl;v 23-19zl 41Claims.

The present' inventi'on relates` toV a process for the separation of zi'rconium and hafnium. More particularly, it' relates to an ion-exchange process forv separating zirconium and haf'nium'from each other.

' The chemistry of zirconium is remarkably' similar to that of hafnium'; any compound formed by the one element appears to be' formed by the other, and, as a rule, the properties'of the two compoundsv are almost identi'cal. In fact, the resemblance is so close between corresponding compounds ofv zirconium and hafnium that it. was not until 1923 that: the presence ofseveral percent hafnium was discovered' in apparently'pure" zirconium compounds.

s a consequence of this similarity, separations of zirconium and hafniuml in the past have left much to be' desired from the standpoint of the time and labor required and; the purities achieved. Such previous separations have,l in general; made use of tedius and involved procedures like fractional precipitati'ons. and' fractional crystallizations of'various zirconium` and hafni- 'um compounds.

Now, it has been found that certain resins commonly known as' ion exchange resins may be employed under certain conditionsto effect a; very efiicient and inexp'ensive separation of' zirconium and' hafnium.

It' is thereforea principal Qbjectofthepresent invention to providea simple, prac'tical,`v and' em.- cient` method of 'separatin-g. irconium and hafnium from each other.

Another object of the invention isl to decrease the amount of labor, materials, and time employed in theseparation of zi'rconium. and hafnium. v. A furthei: object of the inventimr is toutili'ze 'ion exchange resins, to provide a separation of zirconium and' hafnium.

Other objects and advantages'will be apparent from the following description considered'together with the attached: drawing;4 which comprises agraph illustrating results. obtained in. a, typicalseparation of. the two elements in accordance with the invention.

It-has. been known for some time thatcertain resins. exhibitvery pronounced and selective adsorpfiion properties for; al large number of ionic substances. such resins are, termed ion exchange resins and are-essentiallyresinous materials, whichl possess numerous reactive groups capable offexchanging their ionizable. components forother` ions of the same; sign.v Ion exchange resins are further classified as cationic 2'; and'fianionic exchange resins according to-whether they exchange cations or' anions.f

Cationic exchange'resins, which are; particularly suited for use in the processes ofA the present inventionl,` possess reactive groups suchz as -SO8X, -COOX, and the like inwhich the ion.- izable components X (e. g., Hi, NH4+, etc.)k is capable of being replaced by'iother cationic species. The treatment of atypica-l cationi'c lexchange resin' inv the ammonium form (i. e., NH4+ isthe replaceable cation)l with an acidi'c: solutiontoV convertthe resinto the acid form may be represented the following equat'ioii:L

seQuence, have high adsorptiveproperties.

In general, separatioir processes usingv ionv ex'- change resins comprise adsorbingl the: ionsV tol be separated on an ion exchange resin andithereafter selectivelyeluting the ions' from the' resin. More specifically', a Solution of ions to bev separated is passed through a column of' finely' divided exchange resin'under` such conditions thatv the ions areremoved from'the solution andv adsorbed' on the resin by undergoi-ngA ion exchangewithv the resin. Anv elu'ting solution; characterized' by forming'complexes ofidiffering stability-'with each ion, is thenpassedv through` the column:` Since there willV exist a competitionbetweenl the resin and eluting solution for each ion, providing the flow rate of the eluting: solution is not too high, each ion will go through many resin-solution equilibria as vit passes down'the'column. Inthis respect, the operation; of an ion` exchange column may be considered to be analogous, to thev operationfof, an, eflijcient fraotnting column Whr'ein the many equlibrium stages give; a. large enough magnincation of; minutev comPOnent. differences to make. possible the separation ofv components with almost tidenticali Droperties-` Therate at which each of the. ionsmoves down the column upon elution will, in general, depend e into bands Will be effected as they travel down the column. Separate fractions of the eluting solution, each enriched in a particular constituent, may thus be collected. Moreover, the nature of the eluting agent and the conditions of operation of the column are specific and critical with respect to' the separation of zirconium and haf- I have found it advantageous in the practice of my invention to equilibrate a separate portion of' cationic exchange resin with a solution containing hafnium and zirconium, instead of adsorbing the said elements by passage of a solution containing them through a column of resin as described above. (However, this latter procedure may be used if desired.) More speoifically, a cationic exchange resin is rst slurried with a perchloric acid solution and then quantities of a mixture of hafnium and zirconium, preferably as their oxychlorides, are added with thorough stirring to the slurry. The resulting equilibrated resin slurry is then placed on top of a Vcolumn previously packed with the same resin in the acid form (i. e., I-I+ is lthe replaceable cation). It is readily apparent that in this method of adsorption 'the adsorbed hafnium and zirconium are located in a rather sharply defined region, Vnamely the column volume occupied by the equilibrated portion of the resin.

Enoughiresin should be used in the equilibration step to insure that the adsorption capacity of .t,he resin is sufiicient to allow for maximum adsorption of the ionic materials. The. resin should be finely divided to present the maximum surface to the solution, care being taken to keep the particle size from being so small as to cause the resin to pack "solid" and inhibit the flow of solutions through the column. A particle size corresponding to U. S. mesh 250-500 has been found to be satisfactory.

It has been found that aqueous hydrochloric acid solutions are suitable for the elution of the hafnium and zirconium from the resin column, the hafniumv being eluted, first. Excellent separationshave been achieved using concentration of hydrochloricacid in the range 5.5-6 molar and .a'fiow rate of acid through the column of 0.1-0.3 -ml./cm.2/min. As the concentration of the acid raised above l6 molar, the hafnium and -zirconium tend to come off together. At lower concentrations of acid (down to 3 molar) a separation of hafnium and zirconium is still achieved, V but the time required to remove the elements from the column becornes long.

The following example, involving milligram quantities of materaLdIluStrates the process of my invention and its applicability to the produc- .tion of significant amounts of pure hafnium and :'zrconium.

Eample t 'Thirty-'five mg. of zirconium oxide and mg. 'of hafnium oxide were dissolved in a mixture of Vsulfuric and hydrofluoric acids, hafnium and zirconium tracer (I-If181 and Zr95) added, and the mixture fumed to dryness. The residue was taken up in concentrated hydrochloric acid and the hydroxides precipitated with ammonium hydrox- 'ide and washed. The hydroxides were again dissolved in hydrochloric acid and the oxychlorides `o rystalli'zed by evaporation. One c. c. of 2507to-v 'r 500 mesh Dowex 50 sph'eres (a cationic exchange vresin of thejtype described above) in the am- 1 monium form, were suspended in 30 c. c.'of 2 M perchloric acidvand the mixed oxychlorides added the eluate containing separate a few mg. at a time over a period of 15 minutes, the mixture being continually agitated by bubbling air through it. Under these conditions, i. e., approximately 0.01 M zirconium and hafnium in 2 M perchloric acid, the zirconium and hafnium are not appreciably polymerized and about of each is adsorbed by the resin. The slurry of resin WjaS placed 'on the top of zan ionexchange column 1 sq. cm. in area and 30 cm. long which previously had been packed with the same resin and washed with 6 M hydrochloric lacid to convert it to the acid form. On elution With 6 molar hydrochloric acid at a fiow rate of approximately 0.1 ml./cm.2/min., the elution curve shown in the attached drawing was obtained. The outline of the curve was obtained by counting the tracers (Zr and Hfmv) and the dotted portions by optical spectrographic analysis. The use of the radioactive tracer technique greatly simplified the determination of the eluate fractions containing the separated hafnium and zirconium. It can be seen `by graphicalintegration of the area under the aforementioned curve that approximately 10 mg. of hafnium (asoHfOz) containing less than 0.1% ZrOz was obtained in the eluate fraction from 53 ml. to 72 ml.l In the eluate fraction from 86 ml. to ml. approximately 28 mg. of Zr (as ZrOz) was obtained'containing 1ess than 05% Hfoz.

The term "eluate" or its equivalent, as used herein, is intended to include any effluent bearing a desired product from a bed of adsorbent.

The term eluting agent." elutriantfi' o r equivalent, is intended to include a i material which removes adsorbed material from a bedtof adsorbent. o

The term 'adsorption is utilized in referring to removal ofcomponents 'from solutions ba solid. material.

While the salient features of this invention havebeen described in detail with respect to one embodiment it will, of course, be apparent that numerous modifications may be made within the spirit and scope of this invention and it is ,not therefore desired to limit the invention to the exact details except insofar as they may Abedefined in the following claims. i' What is claimed is: 1. In a method for separating the elements zirconium and hafnium from each other, the steps comprising contacting an aqueous solution containing said elements in ionic form with a cationic exchange resin, selectively eluting said elements from said resin with a hydrochloric acid solution 4wherein the concentration of Vthehylrochloric acid is in the range of about 3 to' fl'nola'r, and collecting fractions of the eluate contai the separated elements. i 2. In a method for separating the elements zirconium and hafnium from each other, the steps comprising eguilib'rating a mixture of said elements in ionic form withian acidic slurry o fa cationio exchange resin, placing said equilibrated resin slurry containing the adsorbed zirconium and hafnium upon a column partially filled'wit'h the same resin in the acid form, eluting said elevments from said resin-filled column with a hydrochloric acid solution Wherein the concentration of thehydrochloric acid is in the range' of about 3 to 6` molar, and collecting fractions 'of said elutd elements as' fractional products.

In a method for separating the elements 'zirconium and hafnium from each other'ff th v,'`75

steps comprising equilibrating a'mixture elements as their oxychlorides with a perchloric acid slurry of a cationic exchange resin, placing said equilibrated resin slurry containing the adsorbed zirconium 'and hafnium upon a column partially filled with the same resin in the acid form, eluting said elements from said resin-filled column with a hydrochloric acid solution wherein the concentraton of the hydrochloric acid is in the range of about 3 to 6 molar, and collecting fractions of the eluate containing said eluted elements as separate fractional products.

4. In a method for separating hafnium and zirconium by ymeans of a cationic exchange resin. the step comprising eluting the adsorbed zirconium and hafnium With a hydrochloric acid solution having a concentration in the range of 'about 3 to 6 molar.

KENNETH STREET, J R.

REFERENCES CITED The following references are of record in the file of this patent:

Kraus, K. A. and Moore, G. Journal American Chemical Society, 71, 1949, page 3263.

Street, Kenneth, Jr., and Seaborg, G. T., Journal American Chemical Society, 70, 1948, pages 4268-9. 

1. IN A METHOD FOR SEPARATING THE ELEMENTS ZIRCONIUM AND HAFNIUM FROM EACH OTHER, THE STEPS COMPRISING CONTACTING AN AQUEOUS SOLUTION CONTAINING SAID ELEMENTS IN IONIC FORM WITH A CATIONIC EXCHANGE RESIN, SELECTIVELY ELUTING SAID ELEMENTS FROM SAID RESIN WITH A HYDROCHLORIC ACID SOLUTION WHEREIN THE CONCENTRATION OF THE HYDROCHLORIC ACID IS IN THE RANGE OF ABOUT 3 TO 6 MOLAR, AND COLLECTING FRACTIONS OF THE ELUATE CONTAINING THE SEPARATED ELEMENTS. 